CN103540921B - A kind of electrogalvanizing environmental protection passivating solution - Google Patents
A kind of electrogalvanizing environmental protection passivating solution Download PDFInfo
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- 230000007613 environmental effect Effects 0.000 title claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 7
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 7
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 238000002161 passivation Methods 0.000 abstract description 49
- 238000009713 electroplating Methods 0.000 abstract description 12
- 238000005246 galvanizing Methods 0.000 abstract description 10
- 150000003839 salts Chemical class 0.000 abstract description 6
- 239000011701 zinc Substances 0.000 abstract description 6
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 230000007935 neutral effect Effects 0.000 abstract description 5
- 239000007921 spray Substances 0.000 abstract description 5
- 229910052725 zinc Inorganic materials 0.000 abstract description 5
- 239000007769 metal material Substances 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 10
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 5
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Chemical group 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010959 steel Chemical group 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002265 redox agent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Chemical Treatment Of Metals (AREA)
Abstract
本发明涉及一种电镀锌环保钝化液，属金属材料表面处理技术领域。该钝化液的组分为20～30g/L硅酸钠、10～20mL/L双氧水、20～30g/L硝酸锌、6～10g/L氟化钠、9～15g/L硫酸铜、3～5mL/L硫酸、其余为水，pH值为2.5～3。该钝化液完全符合我国电镀废水排放标准和欧盟RoHS指令等环保标准。使用本钝化液进行处理后的锌镀层外观为均匀彩虹色钝化膜，经中性盐雾试验出白锈时间超过72小时。The invention relates to an environmentally friendly passivation solution for electro-galvanizing, which belongs to the technical field of metal material surface treatment. The components of the passivation solution are 20-30g/L sodium silicate, 10-20mL/L hydrogen peroxide, 20-30g/L zinc nitrate, 6-10g/L sodium fluoride, 9-15g/L copper sulfate, 3 ～5mL/L sulfuric acid, the rest is water, and the pH value is 2.5～3. The passivation solution fully complies with my country's electroplating wastewater discharge standards and EU RoHS directives and other environmental standards. The appearance of the zinc coating treated with this passivation solution is a uniform iridescent passivation film, and the white rust time is more than 72 hours after the neutral salt spray test.
Description
技术领域technical field
本发明涉及一种电镀锌环保钝化液，主要用于钢铁零件表面电镀锌的后处理工序，该钝化液无铬且不含重金属及有机物，属金属材料表面处理技术领域。The invention relates to an electro-galvanizing environment-friendly passivation solution, which is mainly used in the post-treatment process of electro-galvanizing on the surface of iron and steel parts. The passivation solution is chromium-free and does not contain heavy metals and organic substances, and belongs to the technical field of metal material surface treatment.
背景技术Background technique
镀锌是目前国内外提高钢铁耐蚀性的重要手段之一，广泛用于航空、机械、建筑、交通等领域。但是镀锌层在空气中尤其是在潮湿的环境中，极易被腐蚀，为了满足在恶劣环境中的耐蚀要求，需钝化处理来达到耐蚀性标准。Galvanizing is one of the important means to improve the corrosion resistance of steel at home and abroad, and it is widely used in aviation, machinery, construction, transportation and other fields. However, the galvanized layer is easily corroded in the air, especially in a humid environment. In order to meet the corrosion resistance requirements in harsh environments, passivation treatment is required to meet the corrosion resistance standards.
现在，最常用的工业钝化处理工艺为铬酸盐钝化。铬酸盐钝化工艺简单、成本较低，其钝化膜结合力好，具有优良的抗腐蚀性能。但是钝化液中的六价铬有毒可致癌，对环境有很大破坏。所以，近年来人们逐渐开发低毒性或无毒性的钝化液来替代铬酸盐，降低对人体和环境的伤害。Now, the most commonly used industrial passivation treatment process is chromate passivation. The chromate passivation process is simple, the cost is low, the passivation film has good bonding force, and has excellent corrosion resistance. However, the hexavalent chromium in the passivation solution is toxic and can cause cancer, which has great damage to the environment. Therefore, in recent years, people have gradually developed low-toxic or non-toxic passivation solutions to replace chromate to reduce harm to the human body and the environment.
中国申请200710009302.5公开了“一种无铬钝化液”，该方案用35～40g有机酸、20～25g无机盐、0.8～1g表面剂、4～5g氧化剂与无机酸配制成PH为2～5的钝化液，无机物与有机物结合，其耐蚀性与铬酸盐相当。Chinese application 200710009302.5 discloses "a chrome-free passivation solution". The solution uses 35-40g of organic acid, 20-25g of inorganic salt, 0.8-1g of surface agent, 4-5g of oxidant and inorganic acid to prepare a pH of 2-5 The passivation solution, the combination of inorganic matter and organic matter, its corrosion resistance is equivalent to that of chromate.
中国申请101956190 A公开了“一种镀锌层彩虹色钝化剂的制备及钝化工艺”，改方案采用3～10g/L CrO3 、4～9g/L NaCl、lg/L KCl混合，用4～6mL 醋酸调节PH到1～1.2获得的钝化液，使用该钝化液获得的钝化膜红度高，平整性好。Chinese application 101956190 A discloses "a preparation and passivation process of an iridescent passivator for galvanized layer", and the modified scheme adopts 3-10g/L CrO3, 4-9g/L NaCl, 1g/L KCl to mix, and use 4 ~6mL of acetic acid to adjust the pH to 1~1.2 to obtain the passivation solution. The passivation film obtained by using this passivation solution has high redness and good flatness.
中国申请102002697 A公开了“无铬钝化液”，该方案使用游离元素形成的盐20～35克、络合剂18～38克、氧化还原剂0.05～0.15克与水配合，该钝化液钝化工艺与铬酸盐钝化工艺相同，节省了企业的工人培训费用。Chinese application 102002697 A discloses a "chromium-free passivation solution", which uses 20-35 grams of salt formed by free elements, 18-38 grams of complexing agent, 0.05-0.15 grams of redox agent and water, the passivation solution The passivation process is the same as the chromate passivation process, which saves the company's worker training costs.
与上述专利相比，本发明钝化液不含有机物，用无机物配制而成，对环境的伤害更小，成本更低，有利于生产与排放。Compared with the above-mentioned patents, the passivation solution of the present invention does not contain organic matter and is formulated with inorganic matter, which has less damage to the environment, lower cost, and is conducive to production and discharge.
发明内容Contents of the invention
本发明为了克服现有的镀锌钝化技术的不足，提供一种电镀锌环保钝化液，无铬不含重金属，达到国家排放标准的电镀锌环保彩色钝化剂。配制过程简单，易于操作，并且废水处理简单，不易引起环境二次污染。In order to overcome the deficiencies of the existing galvanizing passivation technology, the present invention provides an electro-galvanizing environmental protection passivation solution, which is chromium-free and heavy metal-free, and which meets the national discharge standard. The preparation process is simple, easy to operate, and the waste water treatment is simple, which is not easy to cause secondary environmental pollution.
本发明的技术方案是：该钝化液的组分为20～30g/L硅酸钠、10～20mL/L双氧水、20～30g/L硝酸锌、6～10g/L氟化钠、9～15g/L硫酸铜、3～5mL/L硫酸、其余为水，pH值为2～3。The technical scheme of the present invention is: the component of this passivation solution is 20～30g/L sodium silicate, 10～20mL/L hydrogen peroxide, 20～30g/L zinc nitrate, 6～10g/L sodium fluoride, 9～ 15g/L copper sulfate, 3-5mL/L sulfuric acid, the rest is water, the pH value is 2-3.
本发明钝化液的配制过程为：将上述组分的硅酸钠放入在水中，滴加硫酸搅拌直至硅酸钠溶解，然后依次加入硝酸锌、双氧水和硫酸铜，溶解后再滴加硫酸至酸性，最后将氟化钠溶于溶液，用硫酸调整pH为2～3。The preparation process of the passivation solution of the present invention is: put the sodium silicate of the above components into water, add sulfuric acid dropwise and stir until the sodium silicate dissolves, then add zinc nitrate, hydrogen peroxide and copper sulfate in sequence, and then add sulfuric acid dropwise after dissolving until acidic, and finally dissolve sodium fluoride in the solution, and adjust the pH to 2-3 with sulfuric acid.
本发明的有益效果：该钝化液完全符合我国电镀废水排放标准和欧盟RoHS指令等环保标准。使用本钝化液进行处理后的锌镀层外观为均匀彩虹色钝化膜，经中性盐雾试验出白锈时间超过72小时。Beneficial effects of the present invention: the passivation solution fully complies with my country's electroplating wastewater discharge standards and EU RoHS directives and other environmental protection standards. The appearance of the zinc coating treated with this passivation solution is a uniform iridescent passivation film, and the white rust time is more than 72 hours after the neutral salt spray test.
具体实施方式detailed description
下面结合具体实施方式，对本发明作进一步说明。The present invention will be further described below in combination with specific embodiments.
实施方式一：本发明的该钝化液的组分为20g/L硅酸钠、10mL/L双氧水、20g/L硝酸锌、6g/L氟化钠、9g/L硫酸铜、3mL/L硫酸、其余为水，pH值为2。Embodiment 1: The components of the passivation solution of the present invention are 20g/L sodium silicate, 10mL/L hydrogen peroxide, 20g/L zinc nitrate, 6g/L sodium fluoride, 9g/L copper sulfate, 3mL/L sulfuric acid , the rest is water, the pH value is 2.
该钝化液用于对80mm×80mm×1.5mm A3低碳钢进行硅酸盐钝化处理。低碳钢在进行电镀之前进行打磨除锈、除油、活化等前处理后，放入电镀液中进行电镀，镀锌工艺的镀液组成及操作条件为：ZnCl2 80 g/L、NaCl200 g/L 、硼酸30g/L，镀锌添加剂适量、镀液的pH值保持在4.5左右，电流密度为1.0 A/ dm2，室温，电镀时间约为20分钟。电镀后将零件取出用自来水清洗，然后放入由1％HNO3和H2O组成的出光液中停留3秒，取出低碳钢用水清洗干净，再用本钝化液在室温下钝化80s处理，最后将低碳钢清洗干净并用吹恒温甩干机干燥低碳钢表面水分。The passivation solution is used to carry out silicate passivation treatment on 80mm×80mm×1.5mm A3 low carbon steel. Before electroplating, low-carbon steel is subjected to pretreatments such as grinding, derusting, degreasing, activation, etc., and then placed in electroplating bath for electroplating. The bath composition and operating conditions of the galvanizing process are: ZnCl 2 80 g/L, NaCl 200 g /L, boric acid 30g/L, appropriate amount of galvanizing additives, the pH value of the plating solution is maintained at about 4.5, the current density is 1.0 A/dm 2 , room temperature, and the electroplating time is about 20 minutes. After electroplating, take the parts out and wash them with tap water, then put them into the light-emitting solution composed of 1% HNO 3 and H 2 O for 3 seconds, take out the low-carbon steel and wash them with water, and then use this passivation solution to passivate at room temperature for 80s Finally, clean the low-carbon steel and dry the surface moisture of the low-carbon steel with a constant temperature dryer.
使用本钝化液进行处理后的锌镀层外观为均匀红绿色钝化膜，经中性盐雾试验出白锈时间超过70小时。The appearance of the zinc coating treated with this passivation solution is a uniform red-green passivation film, and the white rust time is more than 70 hours after the neutral salt spray test.
实施方式二：本发明的该钝化液的组分为25g/L硅酸钠、15mL/L双氧水、25g/L硝酸锌、8g/L氟化钠、12g/L硫酸铜、4mL/L硫酸、其余为水，pH值为2.5。Embodiment 2: The components of the passivation solution of the present invention are 25g/L sodium silicate, 15mL/L hydrogen peroxide, 25g/L zinc nitrate, 8g/L sodium fluoride, 12g/L copper sulfate, 4mL/L sulfuric acid , the rest is water, the pH value is 2.5.
该钝化液用于对与某跳伞安全扣电镀Zn后的硅酸盐钝化处理。安全扣经前处理（除锈、除油、活化）后实施电镀，锌铁合金电镀工艺的镀液组成及操作条件为：NaOH 100 g/L 、ZnCl210 g/L、添加剂适量、pH值12.5、阴极电流密度 1.7A/dm2、温度为室温，电镀时间为30分钟。电镀后将安全扣取出并用水清洗干净，然后放入由1％HNO3 ml/L和H2O组成的出光液中停留5秒，取出零件用水清洗干净，再用本钝化液室温下钝化处理40秒，最后将安全扣放入大型烘箱干燥零件表面水分。The passivation solution is used to passivate the silicate after Zn plating with a parachuting safety buckle. The safety buckle is electroplated after pretreatment (rust removal, degreasing, activation). The bath composition and operating conditions of the zinc-iron alloy electroplating process are: NaOH 100 g/L, ZnCl 2 10 g/L, appropriate amount of additives, pH value 12.5 , the cathode current density is 1.7A/dm 2 , the temperature is room temperature, and the electroplating time is 30 minutes. After electroplating, take out the safety buckle and clean it with water, then put it in the light-emitting solution composed of 1% HNO 3 ml/L and H 2 O for 5 seconds, take out the parts and clean them with water, and passivate them with this passivation solution at room temperature chemical treatment for 40 seconds, and finally put the safety buckle into a large oven to dry the surface moisture of the part.
使用本钝化液进行处理后的锌镀层外观为均匀彩虹色钝化膜，经中性盐雾试验出白锈时间超过78小时。The appearance of the zinc coating treated with this passivation solution is a uniform iridescent passivation film, and the white rust time is more than 78 hours after the neutral salt spray test.
实施方式三：本发明的该钝化液的组分为30g/L硅酸钠、20mL/L双氧水、30g/L硝酸锌、10g/L氟化钠、15g/L硫酸铜、5mL/L硫酸、其余为水，pH值为3。Embodiment 3: The components of the passivation solution of the present invention are 30g/L sodium silicate, 20mL/L hydrogen peroxide, 30g/L zinc nitrate, 10g/L sodium fluoride, 15g/L copper sulfate, 5mL/L sulfuric acid , the rest is water, the pH value is 3.
用该钝化液用于对螺丝、螺帽等五金零件镀锌后的钝化处理。五金零件经前处理（除锈、除油、活化）后实施滚镀，镀锌工艺的镀液组成及操作条件为： ZnCl2 70 g/L、KCl190g/L、添加剂适量、pH值5.5、阴极电流密度 1.2 A/dm2、温度为室温，电镀时间为60分钟。电镀后将五金零件取出并用水清洗干净，然后放入由1％ HNO3和H2O组成的出光液中停留2秒，取出五金零件用水清洗干净，再用本钝化液室温下钝化处理60秒，最后将钢板清洗干净并送入离心干燥机甩干零件表面水分。Use this passivation solution for passivation treatment of hardware parts such as screws and nuts after galvanizing. Metal parts are subjected to barrel plating after pretreatment (rust removal, degreasing, activation). The bath composition and operating conditions of the galvanizing process are: ZnCl 2 70 g/L, KCl 190g/L, appropriate amount of additives, pH value 5.5, cathode The current density is 1.2 A/dm 2 , the temperature is room temperature, and the electroplating time is 60 minutes. After electroplating, take out the hardware parts and clean them with water, then put them into the light-emitting solution composed of 1% HNO 3 and H 2 O for 2 seconds, take out the hardware parts and clean them with water, and passivate them with this passivation solution at room temperature 60 seconds, finally clean the steel plate and send it to the centrifugal dryer to dry the surface moisture of the parts.
使用本钝化液进行处理后的锌镀层外观为均匀彩虹色钝化膜，经中性盐雾试验出白锈时间超过75小时。The appearance of the zinc coating treated with this passivation solution is a uniform iridescent passivation film, and the white rust time is more than 75 hours after the neutral salt spray test.
以上对本发明的具体实施方式作了详细说明，但是本发明并不限于上述实施方式，在本领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。The specific embodiments of the present invention have been described in detail above, but the present invention is not limited to the above embodiments, and various changes can be made without departing from the gist of the present invention within the scope of knowledge possessed by those of ordinary skill in the art .
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310518874.1A CN103540921B (en) | 2013-10-29 | 2013-10-29 | A kind of electrogalvanizing environmental protection passivating solution |
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| 杨晓科.镀锌层硅酸盐无铬彩色钝化工艺研究.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2013,(第3期),第13页表3.1，第14页第2段，第16页第1段，第22页第1段，摘要. * |
| 林萍.镀锌层的硅酸盐无铬钝化研究.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2012,(第03期),第20页表3-1，第26页末段-第27页第1段，第33页末段-第34页第1段. * |
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